N-N-Dimethyl-1-(1&#39;-methyl-2&#39;-methoxyethyl)-1,2,4-triazolylcarbamates

ABSTRACT

Triazolylcarbamates of the formula ##STR1## wherein R 1  is hydrogen, chlorine, C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy or C 1  -C 4  -alkylthio, processes for producing them, and their use for combating insect pests.

The present invention relates to triazolylcarbamate derivatives, toprocesses for producing them, and to their use for combating insectpests.

The triazolylcarbamate derivatives have the following formula ##STR2##wherein R₁ is hydrogen, chlorine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁-C₄ -alkylthio.

The alkyl groups denoted by R₁ can be straight-chain or branched-chain.Examples of such groups are, inter alia: methyl, methoxy, methylthio,ethyl, ethoxy, ethylthio, n-propyl, n-propoxy, n-propylthio, n-, i-,sec- or tert-butyl, n-butoxy, i-propyl, n-butylthio, isopropoxy andiso-propylthio.

The compounds of the formula I can be produced by methods known per se,for example as follows: ##STR3##

In the formulae II to IV, the symbol R₁ has the meaning defined underthe formula I, "Hal" is halogen, preferably chlorine or bromine, and"Me" denotes a metal, particularly an alkali metal, ammonium ortrialkylammonium.

Suitable acid-binding agents are for example the following bases:tertiary amines, such as triethylamine, dimethylaniline or pyridine; andinorganic bases, such as hydroxides and carbonates of alkali metals andalkaline-earth metals, preferably sodium and potassium carbonate.

The processes A and B are performd at a reaction temperature of 0°-120°C., preferably at 20°-80° C., under normal pressure, and in solvents ordiluents. Suitable solvents or diluents are for example: ethers andethereal compounds, such as diethyl ether, dipropyl ether, dioxane,dimethoxyethane and tetrahydrofuran; amides, such as N,N-dialkylatedcarboxylic acid amides; aliphatic, aromatic as well as halogenatedhydrocarbons, particularly benzene, toluene, xylenes, chloroform andchlorobenzene; nitriles, such as acetonitrile; dimethyl sulfoxide; andketones, such as acetone or methyl ethyl ketone; and water.

The compounds of the formula I are suitable for combating various animaland plant pests. The compounds thus have for example nematicidal,fungicidal and bactericidal activity.

The compounds of the formula I are especially suitable for combatinginsects, phytopathogenic mites and ticks, for example of the orders:Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Acarina,Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura,Isoptera, Psocoptera and Hymenoptera. The compounds of the formula I aresuitable in particular for combating insects that damage plants,especially insects that damage plants by eating, in crops of ornamentalplants and useful plants, particularly in cotton crops (for exampleagainst Spodoptera littoralis and Heliothis virescens), and in crops ofvegetables (for example against Leptinotarsa decemlineata and Myzuspersicae). Active substances of the formula I have a very favourableaction also against flies, such as Musca domestica, and against mosquitolarvae.

The acaricidal and insecticidal action can be substantially broadenedand adapted to suit given circumstances by the addition of otherinsecticides and/or acaricides. Suitable additives are for example:organic phosphorus compounds; nitrophenols and derivatives thereof;formamidines; ureas; pyrethrin-like compounds; as well as othercarbamates and chlorinated hydrocarbons.

Compounds of the formula I are combined particularly advantageously alsowith substances which have a hydrotropic effect. Examples of compoundsof this kind are, inter alia: piperonylbutoxide, propynyl ethers,propynyl oximes, propynyl carbamates and propynyl phosphonates,2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane (Sesamex orSesoxane), S,S,S-tributylphosphorotrithioates and1,2-methylenedioxy-4-(2-(octylsulfonyl)-propyl)-benzene.

Compounds of the formula I can be used on their own or together withsuitable carriers and/or additives. Suitable carriers and additives canbe solid or liquid and they correspond to the substances common informulation practice, such as natural or regenerated substances,solvents, dispersing agents, wetting agents, adhesives, thickeners,binders and/or fertilisers.

The compositions according to the invention are produced in a mannerknown per se by the intimate mixing and/or grinding of the activesubstances of the formula I with suitable carriers, optionally with theaddition of dispersing agents or solvents which are inert to the activesubstances. The active substances can be obtained and used in thefollowing forms:

solid preparations

dusts, scattering agents, granules (coated granules, impregnatedgranules and homogeneous granules);

liquid preparations

(a) water-dispersible concentrates of active substance: wettablepowders, pastes or emulsions;

(b) solutions.

The content of active substance in the compositions described above isbetween 0.1 and 95%; it is to be mentioned in this respect that withapplication from an aeroplane, or from other suitable devices,concentrations of up to 99.5% or even the pure active substance can beused.

The active substances of the formula I can be formulated for example asfollows (parts are by weight).

Dusts

The following substances are used to produce (a) a 5% dust and (b) a 2%dust:

(a)

5 parts of active substance, and

95 parts of talcum; and

(b)

2 parts of active substance,

1 part of highly dispersed silicic acid, and

97 parts of talcum.

The active substance is mixed and ground with the carriers.

Granulate

The following ingredients are used to produce a 5% granulate:

5 parts of active substance,

0.25 part of epoxidised vegetable oil,

0.25 part of cetyl polyglycol ether,

3.50 parts of polyethylene glycol, and

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and the mixture isdissolved in 6 parts of acetone; the polyethylene glycol and cetylpolyglycol ether are then added. The solution thus obtained is sprayedonto kaolin, and the acetone is subsequently evaporated off in vacuo.

Wettable powders

The following constituents are used to produce (a) a 40% wettablepowder, (b) and (c) a 25% wettable powder and (d) a 10% wettable powder:

(a)

40 parts of active substance,

5 parts of sodium lignin sulfonate,

1 part of sodium dibutyl-naphthalene sulfonate, and

54 parts of silicic acid;

(b)

25 parts of active substance,

4.5 parts of calcium lignin sulfonate,

1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutyl-naphthalene sulfonate,

19.5 parts of silicic acid,

19.5 parts of Champagne chalk, and

28.1 parts of kaolin;

(c)

25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol,

1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

8.3 parts of sodium aluminium silicate,

16.5 parts of kieselguhr, and

46 parts of kaolin; and

(d)

10 parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulfates,

5 parts of naphthalenesulfonic acid/formaldehyde condensate, and

82 parts of kaolin.

The active substance is intimately mixed in suitable mixers with theadditives, and the mixture is then ground in the appropriate mills androllers to obtain wettable powders which can be diluted with water togive suspensions of the concentration desired.

Emulsifiable concentrates

The following substances are used to produce (a) a 10% emulsifiableconcentrate, (b) a 25% emulsifiable concentrate and (c) a 50%emulsifiable concentrate:

(a)

10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

3.4 parts of a combination emulsifier consisting of fatty alcoholpolyglycol ether and alkylarylsulfonate calcium salt,

40 parts of dimethylformamide, and

43.2 parts of xylene;

(b)

25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of alkylarylsulfonate/fatty alcohol polyglycol ether mixture,

5 parts of dimethylformamide, and

57.5 parts of xylene; and

(c)

50 parts of active substance,

4.2 parts of tributylphenol-polyglycol ether,

5.8 parts of calcium-dodecylbenzenesulfonate,

20 parts of cyclohexanone, and

20 parts of xylene.

Emulsions of the required concentration can be prepared from theseconcentrates by dilution with water.

Sprays

The following constituents are used to produce (a) a 5% spray and (b) a95% spray:

(a)

5 parts of active substance,

1 part of epoxidised vegetable oil, and

94 parts of ligroin (boiling limites 160°-190° C.); and

(b)

95 parts of active substance, and

5 parts of epichlorohydrin.

The invention is further illustrated by the Examples which follow.

EXAMPLE 1 Production ofN,N-dimethyl-1-(1-methyl-2-methoxyethyl)-5-chloro-1,2,4-triazolylcarbamate

0.1 mol of the compound of the formula ##STR4## with 0.1 mol ofanhydrous pulverised potassium carbonate in 500 ml of methyl ethylketone is heated at 80° C. for four hours. After cooling, there is addedat room temperature 0.1 mol of dimethylcarbamoyl chloride, and thereaction mixture is subsequently stirred at 40° C. for 12 hours. Afterfiltration of the salts and removal of the solvent, recrystallisation ofthe crude product yields the compound of the formula ##STR5## having amelting point of 82°-84° C.

The following compounds are produced in an analogous manner:

    ______________________________________                                         ##STR6##                                                                     R.sub.1                                                                       ______________________________________                                        CH.sub.3          m.p.: 105-106° C.                                    H m.p.:  54-55°  C.                                                    SCH.sub.3         n.sub.D.sup.20°  = 1.5110                            SC.sub.2 H.sub.5  m.p.:  46-48°  C.                                    SC.sub.3 H.sub.7 (i)                                                                            m.p.:  64-67°  C.                                    OCH.sub.3         n.sub.D.sup.20°  = 1.4742                            OC.sub.3 H.sub.7 (i)                                                                            n.sub.D.sup.20°  = 1.4678                            OC.sub.2 H.sub.3  n.sub.D.sup.20°  = 1.4708                            ______________________________________                                    

EXAMPLE 2 (A) Insecticidal stomach-poison action

Cotton plants were sprayed with a 0.05% aqueous emulsion of the activesubstance (obtained from a 10% emulsifiable concentrate).

After drying of the coating, larvae of Spodoptera littoralis in the L₃stage and of Heliothis virescens in the L₃ stage were settled onto thecotton plants. The test was carried out at 24° C. with 60% relativehumidity.

Compounds according to Example 1 exhibited in the above test a goodinsecticidal stomach-poison action against larvae of Spodopteralittoralis and Heliothis virescens,

(B) Systemic insecticidal action

In order to determine the systemic action, rooted bean plants (Viciafaba) were placed into a 0.01% aqueous solution of the active substance(obtained from a 10% emulsifiable concentrate). After 24 hours, beanaphids (Aphis fabae) were placed onto the parts of the plants which hadbeen above the soil. By means of a special device, the bean aphids wereprotected from the effects of contact and of gas. The test was carriedout at 24° C. with 70% relative humidity.

Compounds according to Example 1 exhibited in the above test a systemicinsecticidal action against Aphis fabae.

EXAMPLE 3 Acaricidal action

Phaseolus vulgaris plants were infested, 12 hours before the test foracaricidal action, with an infested piece of leaf from a mass culture ofTetranychus urticae. The transferred mobile stages were sprayed with theemulsified test preparations from a chromatography-sprayer in a mannerensuring no overflow of the spray liquor. An assessment was made after 2and 7 days, respectively, by examination under a binocular microscope,of the living and of the dead larvae, adults and eggs, and the resultswere expressed as percentages. The treated plants were kept during theholding time in greenhouse compartments at 25° C.

Compounds according to Example 1 exhibited in the above test a goodaction against adults, larvae and eggs of Tetranychus urticae.

EXAMPLE 4 Action against soil nematodes

In order to test their action against soil nematodes, the activesubstances were added to soil infested with root-gall nematodes(Meliodogyne arenaria), and intimately mixed with the soil. In one testseries, tomato seedlings were planted immediately after preparation ofthe soil in the manner described, and in the other test series tomatoeswere sown after a waiting time of 8 days. An assessment of thenematocidal action was made by counting the galls present on the roots28 days after planting and sowing, respectively.

Active substances according to Example 1 exhibitied in this test a goodaction against Meloidogyne arenaria.

EXAMPLE 5 Action against ticks

(A) Rhipicephalus bursa

For each concentration, 5 adult ticks and 50 tick larvae, respectively,were counted into a small glass test tube, and immersed for 1 to 2minutes in 2 ml of an aqueous emulsion from a dilution series of 100,10, 1 and 0.1 ppm of test substance. The tubes were then sealed with astandardised cotton plug, and inverted so that the active-substanceemulsion could be absorbed by the cotton wool.

The evaluation in the case of the adults was made after 2 weeks and inthe case of the larvae after 2 days. There were two repeats for eachtest.

(B) Boophilus microplus (larvae)

With a dilution series analogous to that of Test A, tests were carriedout with 20 sensitive larvae and OP-resistant larvae, respectively(resistance is with respect to diazinon compatibility).

Compounds according to Example 1 were effective in these tests againstadults and larvae of Rhipicephalus bursa and against sensitive andOP-resistant larvae, respectively, of Boophilus microplus.

EXAMPLE 6 Action against Erysiphe graminis on Hordeum vulgare

Barley plants about 8 cm in height were sprayed with a spray liquor(0.05% of active substance) produced from wettable powder of the activesubstance. The treated plants were dusted after 48 hours with conidia ofthe fungus. The infested barley plants were placed in a greenhouse atabout 22° C., and the fungus infection was assessed after 10 days.

Compounds according to Example 1 were effective in this test againstErysiphe graminis.

What is claimed is:
 1. A compound of the formula ##STR7## wherein R₁ ishydrogen, chlorine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylthio.2. The compound according to claim 1 of the formula ##STR8##
 3. Thecompound according to claim 1 of the formula ##STR9##
 4. The compoundaccording to claim 1 of the formula ##STR10##
 5. The compound accordingto claim 1 of the formula ##STR11##
 6. The compound according to claim 1of the formula ##STR12##
 7. An insecticidal and acaricidal compositioncomprising a compound according to claim 1 as active ingredient, and acarrier.
 8. A method for combatting insects and acarids which comprisesapplying thereto an insecticidally or acaricidally effective amount of acompound according to claim 1.